Dyeing hair with nitro-substituted phenylene compounds

ABSTRACT

WHEREIN R1 and R2 is each independently a hydrogen atom or lower alkyl, R3 and R4 is each independently C2-C3 hydroxyalkyl, and n is an integer from one to six, are used as dyes for dyeing keratinaceous material.   Nitro-substituted phenylene compounds of the formula

Sohol et a1,

tes

[ Sept. 17, 1974 1 DYIEIING HAIR WIITH NIITRO-SUBSTTTUTED PHENYLENE COMPOUNDS [75] Inventors: Phillip Edward Sokol, Chicago;

Hui-Clio Tsai, Evanston, both of I11.

[73] Assignee: The Gillette Company, Boston,

Mass.

[22] Filed: Nov. 18, 11970 {21] Appl. No.: 90,825

[52] US. Cl 8/110.1, 8/10, 8/178, 260/326, 260/465 E, 260/471 C, 260/558 A, 260/559 A, 421/70 Primary Examiner-Albert T. Meyers Assistant ExaminerVera C. Clarke [5 7] ABSTRACT Nitro-substituted phenylene compounds of the formule wherein R and R is each independently a hydrogen atom or lower alkyl, R and R is each independently C -C hydroxyalkyl, and n is an integer from one to six, are used as dyes for dyeing keratinaceous material.

9 Claims, N0 Drawings DYEING HAIR WITH-I NITRO-SUBSTITUTED PlllllENYLlENE COMPOUNDS BACKGROUND OF THE INVENTION 'and time which can be used are limited to those which can be tolerated by humans and the dye must produce the desired color in the hair with minimal coloring of the skin and scalp. In general, the temperature of the dye composition used on hair can be from room temperature (20 C) up to 45 C and the time for achieving the desired color can be from as little as or minutes to a maximum of about 45 minutes, preferably no more than 30 minutes. The dyeing of textile fibers and fabrics, on the other hand, is frequently carried out at temperatures as high as 100 C for a period of many minutes.

The unique compounds of the present invention are represented by the formula Formula I wherein R and R is each independently selected from the group consisting of a hydrogen atom and lower alkyl, R and R is each independently C C hydroxyalkyl, and n is an integer from one to six.

As used herein, lower alkyl comprehends both straight-chain and branched-chain alkyl groups containing from one to six carbon atoms, e.g. methyl, ethyl, isopropyl, n-butyl, n-hexyl and the like. In a preferred embodiment, R and R each represent a methyl group. Likewise, it will be understood that the term C -C hydroxyalkyl comprehends hydroxyalkyl groups containing from two to three carbon atoms, e.g., hydroxyethyl, hydroxypropyl and and hydroxyisopropyl. In a preferred embodiment, R and R each represents a hydroxyethyl group.

As noted, n represents an integer from one to six. Suitably, n is two to five; most satisfactory products are those in which n represents 2.

Exemplary compounds of Formula I include, for example, N -[2-(N,N-dimethylcarboxamido)ethyl1-2- nitro-N,N"bis-(2-hydroxyethyl)-p-phenylenediamine; N-[2-(N-methylcarboxamido)ethyl]-2-nitro- N,N"-bis-(2-hydroxyethyl)-p-phenylenediamine; N- (Z-carboxamidoethyl )-2-nitro-N,N-bis-( Z-hydroxyethyl)-p-phenylenediamine; N-(5-carboxamidopentyl)- 2 2-nitro-N,N -bis-(2-hydroxyethyl)-pphenylenediamine.

While the nitro-substituted phenylene compounds of Formula I are most useful as dyes for dyeing human hair, they can also be most useful as dyes for dyeing keratinaceous material such as furs, natural protein fibers (e.g., wool, silk, etc.) and synthetic polyamide fibers such as nylon. The compounds of Formula I exhibit strong affinity to hair and other keratinaceous fibers, bond well to such fibers, and are compatible with other known hair dyes so that when used in combination they produce compositions of varying shades.

Still other advantages of the present invention are the provisions of hair dye compositions which can color human hair in a relatively short time at room temperatures and without injury or damage to the hair shaft, skin or scalp.

The compounds encompassed by Formula I can be produced by reacting a compound of the formula 0 R NH(CHa),,- i J-N Formula II wherein R,R and n are as above defined, with a compound selected from the group consisting of ethylene oxide and propylene oxide.

The reaction of a compound of Formula II with ethylene oxide or propylene oxide is conveniently carried out in a reaction medium inert to the reactants such as an inert solvent. The inert solvent can be a lower alkanol (e.g., methanol, ethanol, etc.) or the like. The reaction is suitably carried out at the reflux temperature of the mixture.

The materials of Formula II, employed in the above reaction, can be prepared by any one of several methods. Firstly, the compounds can be: produced by reacting l-chloro-2,4-dinitrobenzene with a compound of Formula VI nxrim cn,),,co cn Formula Vl wherein X is a halogen atom, and n is as above defined, to produce a compound of Formula IV N 0 3 Formula IV wherein n is as above defined, reacting this product with an amine of Formula V Formula V wherein R and R are as above defined, to produce a compound of Formula III mula}? wherein R and R and n are as above defined, and

hydrogenating the product obtained therefrom.

The starting materials of Formula VI are known and have already been described in the literature. For example, the material can be I-ICI.NH (CH;) CO CH The reaction of 1-chloro-2,4-dinitrobenzene with the salt of Formula VI is conveniently carried out in the presence of an acid binding agent. Suitable acid binding agents include alkali metal carbonates, alkali metal bicarbonates, tertiary amines and the like. For example, the acid binding agent can be sodium carbonate, sodium bicarbonate or triethyl amine; preferably sodium bicarbonate is utilized. This reaction can be carried out in an inert organic solvent such as alcohol which is inert to the reactants at the reflux temperature of the mixture. The reaction of a compound of Formula IV with an amine of Formula V is also suitably conducted in an inert solvent such as alcohol at the reflux temperature of the reaction mixture.

Hydrogenation of the product of Formula Ill can be effected using hydrogen in the presence of a noble metal catalyst (e.g., platinum/charcoal, palladium/- charcoal, etc.). The reaction suitably proceeds in the presence of a strong acid (e.g., hydrochloric, sulfuric, etc.) and a lower alkanol (e.g., methanol, ethanol, etc.). In a preferred embodiment, the hydrogenation is effected using platinum/charcoal in the presence of hydrochloric acid and ethanol.

Alternately, some of the materials of Formula II can be prepared by reacting l-chloro-2,4-dinitrobenzene with a compound of Formula VIa 2( 2)7l E Formula VIa wherein n is as above defined, to produce a compound of Formula [Va HIIUCHDUCEN N Formula IVa wherein n is as above defined, hydrolyzing the product to produce a compound of Formula Illa Formula IIIa wherein n is as above defined, and hydrogenating the product obtained therefrom.

The reaction of l-chloro-2,4-dinitrobenzene with a compound of Formula VIa is carried out under the same conditions as the reaction of Formula VI above described.

Hydrolysis of the compound of Formula [Va is conveniently carried out using an aqueous acid such as, for example, aqueous hydrochloric acid. The procedure whereby a compound of Formula [11a is hydrogenated is carried out in a similar manner to that for the hydro genation of Formula III.

For practical use of the compounds of Formula I as hair dyes, it is desirable to formulate them as hair dye compositions comprising as an active ingredient, a tinctorially effective amount of a compound of Formula I in a carrier. For example, a tinctorially effective amount of a compound of Formula I can be incorporated into any of several carriers to produce hair dye compositions such as hair dyes, toners, lotions, shampoos and the like. Such formulations can be in liquid form comprising neutral or alkaline aqueous solutions of the compound of Formula I. Additionally, dye compositions can include conventional ingredients found in hair dye compositions such as organic solvents for the dye, thickeners, detergents, gums and the like.

As used herein, the term carrier comprises a material, preferably a liquid, into which the compo d of Formula I is mixed and which dissolves or dispe s the compound without impairing the effectiveness f the dye and which does not injure or damage the keratinaceous material on which it is used, e.g., hair. Water or organic solvents such as alcohol can be used as a carrier, and mixtures of water with water miscible organic solvents can also be utilized, the organic solvent serving to facilitate solution of the dye. If desired, the dye can be first dissolved in the solvent and then diluted with water. Suitable organic solvents include, for example, lower alkyl monohydric alcohols (e.g., ethanol, isopropanol, etc.), lower aliphatic dihydric alcohols (e.g., ethylene glycol, propylene glycol), and certain polyhydric alcohols, ketones, esters and the like. The dispersion of the various ingredients can be accelerated by the addition of a detergent or dispersing agent such as sodium lauryl sulfate or sodium myristyl sulfate, triethanolamine lauryl sulfate, etc. The water miscible organic solvents utilized to facilitate solution of the dye can vary from about 1 percent to about 30 percent by weight of the composition; preferably from about 2 to about 10 percent. The detergent or dispersing agent can likewise vary from about 1 to about 30 percent by weight of the composition; preferably about 15 percent.

If desired, an alkalizing agent can be added to the hair dye composition to enhance its effectiveness. Suitable alkalizing agents are those which are non-toxic and which do not precipitate the dye or injure the scalp. Sufficient alkalizing agent can be used to produce a composition having a pH of from about 7 to about 12; preferably from 7.5 to 1 1. Suitable alkalizing agents include ammonia derivative alkalizing agents, alkali metal hydroxides, alkaline earth hydroxides and the like. For example, the alkalizing agent can be ammonium hydroxide, a lower alkanolamine (e.g., mono-, di or tri-ethanolamine), lower alkyl amines (e.g., mono or diethyl amine), lower alkylene-diamines (e.g., propylene diamine) or a heterocyclic amine (e.g., morpholine). Where the alkalizing agent is an alkaline earth hydroxide, such hydroxides include calcium hydroxide, magnesium hydroxide, and the like. In a preferred embodiment, the alkalizing agent is diethanolamine.

The hair dye composition of the present invention can be applied to hair using any conventional method of application such as brushing, sponging, dipping, spraying, etc.

The concentration of the active dye ingredient (i.e., compound of Formula I) required in the composition for tinctorial effectiveness varies with the particular kind of hair dye composition and the color desired. Desirably it may range from 0.01 to 1 percent, preferably from 0.05 to percent; in the case of aqueous dye compositions to be applied to human hair on the head, the range is still more preferably from 0.5 to 2 percent.

Although the time of contact of the hair dye composition with the hair is not critical, good results are achieved over a period of time from about 15 minutes to about 45 minutes; preferably about 30 minutes. The temperature of the hair dye composition can vary over temperatures conventional to the art. For example, the temperature of the hair dye composition when applied to the human hair on the head can be from room temperature (i.e. about C) to about 45C.

The following examples are given in further illustration of the invention.

EXAMPLE 1 A solution of 50 g. (0.56 mole) of B-alanine in 300 m1 of methanol was heated to reflux. Hydrogen chloride gas was then introduced into the mixture for 4 hours. The solvent was then removed under vacuum and the resultant syrupy residue dissolved in 50 ml chloroform. Precipitation by addition of diethyl ether to the chloroform solution yielded: methyl-3- aminopropionate hydrochloride.

20.2 g. (0.1 mole) of 1-chloro-2,4-dinitrobenzene and 16.8 g (0.2 mole) sodium bicarbonate was dissolved in 200 m1 of ethanol and 30 ml of water and heated to reflux. 18 g. (0.13 mole) of methyl 3-aminopropionate hydrochloride was then added into the solution while refluxing. After refluxing for 2% hours, the mixture was cooled and filtered. Recrystallization of the precipitate from water methanol yielded: N-(2- carbomethoxyethyl)-2,4-dinitroaniline. m.p. 9296C.

11.3 g. (0.042 mole) of N-(2-carbomethoxyethyl)- 2,4-dinitroaniline was dissolved in 150 ml of methanol and 31.6 g. (0.7 mole) of dimethylamine was then added. The mixture was heated to reflux for 10 hours, cooled and filtered yielding: N-[ 2- (N',N'dimethylcarboxamido)ethyl]-2.4-dinitroaniline. m.p. -143C.

10.2 g. (0.033 mole) of N-[2-(N,N'- dimethylcarboxamido)ethyl]-2,4-dinitroaniline was added to 200 ml of ethanol, 20 ml conc. hydrochloric acid and 0.75 g. of 5 percent platinum on charcoal. The mixture was hydrogenated in a Parr hydrogenator at an actual pressure of 9 psi. at room temperature for 40 minutes. The platinum catalyst was then recovered by filtration. The filtrate was alkalized with concentrated ammonium hydroxide and evaporated to dryness under vacuum. Recrystallization yielded: N'-[2-(N,N- dimethyl carboxamiido)ethyl]-2-nitro-pphenylenediamine. 1.4 g. of N -[2-(N,N-

EXAMPLE 2 A flask containing a mixture of 13.1 g. of 6-amino-nhexanoic acid (0.1 mole) and 14.8 g. (0.1 mole) of phthalic anhydride was heated in an oil bath at C until frothing of the mixture stopped (about 20 minutes). The solid resulting upon cooling was recrystallized from an ethanol/water mixture yielding: 6- phthalimido-n-hexanoic acid. m.p. 8182C.

18.4 g. (0.07 mole) of -phthalimido-n-hexanoic acid was suspended in 250 ml. of benzene and heated to reflux for one hour with a Dean-Stark condenser to remove water in the mixture. 14.65 g. (0.07 mole) of phosphorus pentachloride was then added and the mixture was heated at 60C (water bath) for 30 minutes. The benzene was then removed under vacuum. Recrystallization of the residue from benzene/petroleum ether (b.p. 3060C) yielded: 6-phthalimido-nhexanoyl chloride. m.p. 6468C.

18.1 g. (0.067 mole) of 6-phthalimido-n-hexanoyl chloride was dissolved in 100 ml of dry benzene and added slowly to 30 ml of dimethylamine and the mixture refluxed for 2 hours. The solvent was then removed under vacuum and the residual oil washed with water and dried with anhydrous calcium sulfate. The oil was then heated to reflux for 1 hour with 3.2 g. (0.1 mole) of hydrazine in 250 ml ethanol. After evaporation of the solvent, the dry residue was warmed to 50C for 10 minutes with 200 ml. of 2 N HCL. The mixture was then cooled to room temperature and filtered. Evaporation of the filtrate to dryness and recrystallization from ethanol/water yielded 6-amino-N,N- dimethyl-n-hexamide. m.p. 86-89C.

Using the procedure described in Example 1, N-[S- (N,N'-dimethylcarboxamido)pentyl]-2,4- dinitroaniline was prepared from 2,4-dinitrochloroben= zene and o-amino-N,N-dimethyl-n-hexamide. m.p. 121122C.

EXAMPLE 3 Using the procedure described in Example 1, N -[2- (N,N-dimethylcarboxamido)ethyl]-2-nitro-N, N -bis- (2-hydroxypropyl)-p-phenylenediamine was prepared from N-[2-(N,N-dimethylcarboxamido )ethyl]-2-nitrop-phenylenediamine and propylene oxide in place of ethylene oxide. A max. 520 nm.

EXAMPLE 4 Using the procedure described in Example 1, N -[2- (N-methylcarboxamido)ethyl]-2-nitro-N,N -bis-(2- hydroxyethyl)-p-phenylenediamine was prepared by using monomethylamine in place of dimethylamine. A max. 527 nm.

EXAMPLE 5 Using the procedure described in Example 1, N-[2- (carboxamido)ethyl]-2-nitro-N,N-bis-(2-hydroxyethyl-p-phenylenediamine was prepared by using ammonia'in place of dimethylamine. m.p. l36-l38C. max. 530 nm.

EXAMPLE 6 Using the procedure described in Example 2, N -[5- (carboxamido)pentyl]-2-nitro-N ,N-bis-(2-hydroxyethyl)-p-phenylenediamine was prepared by using ammonia in place of dimethylamine. A max. 535 nm.

EXAMPLE 7 A silver blue toning hair dye composition of medium intensity and suitable for gray hair was prepared containing the following ingredients:

Ingredients Amount Product of Example 1 2 g. Laurie diethanolamide 2 g. Propylene glycol 2 g. Water q.s. 100 g.

The ingredients were mixed together in the order listed above to provide a homogeneous dispersion, and the composition was applied to unbleached natural blonde and unbleached 50 percent gray hair for 30 minutes at a bath to hair ratio of 2.511 by weight at room temperature, producing in each case a light violet tone which did not wash out.

EXAMPLE 8 A silver blue toning dye having a light intensity and suitable for gray hair was prepared having the following composition:

ingredients Amount Product of Example 1 0.5 g. Laurie diethanolamide 2 g. Propylene glycol 2 g. Conc. ammonium hydroxide (28%) 3 g. Water q.s. g.

The composition was prepared and tested as described in Example 7, producing the same results. When applied to the hair for 60 minutes instead of 30, a medium violet tone was produced in each case.

EXAMPLE 9 A silve blue toning dye having a light intensity and suitable for gray hair is prepared having the following composition:

ingredients Amount Product of Example I 2 g. Lauric diethanolamide 2 g. Propylene glycol 2 g. Conc. ammonium hydroxide (28%) 3 g. Water q.s. 100 g.

The composition was prepared and tested as described in Example 7, producing a medium violet tone which did not wash out.

A similar composition in which the amount of active ingredient was 2.5 g. instead of 2 g. produced similar results.

EXAMPLE 10 A hair grooming lotion suitable for gray hair was prepared having the following composition:

Ingredients Amount Product of Example 1 2 g.

Commercial hair setting gel (no color imparted to hair) 98 g.

The ingredients were mixed together to form a homogeneous dispersion, and the composition was applied to unbleached natural blonde and unbleached 50 percent gray hair at room temperature and allowed to remain for 30 minutes, whereupon the composition was rinsed out, leaving a medium violet tone in each case.

EXAMPLE 1 l A silver blue shampoo toner suitable for gray hair was prepared having the following composition:

Ingredients Amount Product of Example l 5 g. Triethanolamine lauryl sulfate (40%) 35 g. Hydroxyethylcellulose 2.5 g. Water 61.5 g.

The ingredients were mixed together in the order named to form a homogeneous dispersion, and the composition was applied to unbleached natural blonde and unbleached 50 percent gray hair atroom temperature. permitted to remain for minutes and rinsed out, producing a light silver shade in each case.

We claim:

l. A hair dye composition comprising an aqueous carrier and as an active ingredient thereof a tinctorially effective amount of a compound of the formula 5. The composition of claim 3 wherein the alkalizing agent is diethanolamine.

6. A method of dyeing hair which method comprises applying to the hair an effective amount of a hair dye composition comprising an aqueous carrier and as an active ingredient thereof a tinctorially effective amount of a compound of the formula wherein R and R is each independently lower alkyl,

R and R is each independently C -C hydroxyalkyl, and n is an integer from one to six. 7. The method of claim 6 wherein the composition further includes an alkalizing agent.

8. The method of claim 7 wherein the alkalizing agent is diethanolamine.

9. The method of claim 6 wherein the tinctorially effective amount of the compound is from about 0.05 to about 5 percent of the weight of said composition. 

2. The composition of claim 1 wherein the compound is N1-(2-(N,N-dimethylcarboxamido)ethyl)-2-nitro-N4,N4-bis-(2-hydroxyethyl)-p -phenylenediamine.
 3. The composition of claim 1 further including an alkalizing agent.
 4. The composition of claim 1 wherein the tinctorially Effective amount of the compound is from about 0.05 to about 5 percent of the weight of said hair dye composition.
 5. The composition of claim 3 wherein the alkalizing agent is diethanolamine.
 6. A method of dyeing hair which method comprises applying to the hair an effective amount of a hair dye composition comprising an aqueous carrier and as an active ingredient thereof a tinctorially effective amount of a compound of the formula
 7. The method of claim 6 wherein the composition further includes an alkalizing agent.
 8. The method of claim 7 wherein the alkalizing agent is diethanolamine.
 9. The method of claim 6 wherein the tinctorially effective amount of the compound is from about 0.05 to about 5 percent of the weight of said composition. 